CN110034279A - A kind of preparation method of flexible lithium ion battery negative electrode material - Google Patents
A kind of preparation method of flexible lithium ion battery negative electrode material Download PDFInfo
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- CN110034279A CN110034279A CN201910380032.1A CN201910380032A CN110034279A CN 110034279 A CN110034279 A CN 110034279A CN 201910380032 A CN201910380032 A CN 201910380032A CN 110034279 A CN110034279 A CN 110034279A
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Abstract
The invention discloses a kind of preparation methods of flexible lithium-ion negative pole.The method is using graphene oxide as active material, it is firstly added conducting polymer monomer, it is aggregated to obtain graphene oxide/conducting polymer composite material, it then sequentially adds with elastomer, conductive agent and the binder that can be bonded with graphene oxide active site, RGO/ conducting polymer/conductive agent/integrated composite material of binder/elastomer is obtained using reduction, finally obtains integrated flexible electrical pole piece by vacuum filtration, dry, roll pressing.For the prepared flexible electrical pole piece obtained of the invention by chemical bonding, intermolecular force is strong, and pole piece material living in bending or charge and discharge process is not easily to fall off, and by vacuum filtration and roll-in, so that each section close contact, plays synergistic effect.Flexible electrode obtained by the present invention has good flexibility and chemical property, and good high rate performance and cycle performance are still being kept after crooked experiment.
Description
Technical field
The present invention relates to a kind of preparation methods of flexible lithium ion battery negative electrode material, belong to lithium ion battery technology neck
Domain.
Technical background
With the problem of environmental pollution for increasing sharply and generating that global energy consumes, the energy of cleaning sustainable development is found
Source becomes the urgent demand of people.For lithium ion battery as important energy storage device due to environmentally protective, environmental pollution is small, and
Have excellent chemical property such as: having extended cycle life, the advantages that capacity is high, self-discharge rate is low, memory-less effect, answer extensively
For the every field of life, such as: flexible display screen, implantable medical devices, mobile phone.Wherein, high-energy density, height are prepared
Active material is not easily to fall off after power density, bending fold and the good flexible lithium ion battery pole piece of cycle performance is by pass
Note.
Traditional electrodes of lithium-ion batteries needs slurry being coated in metal collector surface, i.e. active material and collector
It is connected by binder, this mode not only time and effort consuming, but also active material is often since adhesive strength is inadequate, from
It falls off on collector, the internal resistance of cell is caused to increase, subtract under chemical property.Flexible battery pole piece needs are meeting bending fold
In the case of still keep good chemical property, traditional electrodes of lithium-ion batteries preparation process is unable to reach requirement.
In view of the above-mentioned problems, researcher carries out modified surface, toughening modifying binder to metal collector or using blending
Binder, increase active material viscosity add elastomer in system, coat conductive coating, exploitation on metal collector surface
Flexible paper electrode, carbon cloth do electrode and all kinds of suction filtration film techniques production flexible electrode.Such as Li Feng is in CN 104810504A
Middle to be dispersed with graphene, obtained graphene current collector layers are filtered by vacuum, active electrode material layer is filtered by slurry to graphene
On collector, dry, roll pressing obtains integrated flexible electrode pole piece.Dragon it is good it is equal CN 108417779A using sodium hydroxide/
Urea system makes the form of nanofiber solvent components subchain, then after coagulating bath regeneration method prepare carbon nanotube,
The equally distributed fexible film pole piece of active material, the continuously distributed structure of each component can provide for electrons/ions in the electrode
Excellent transmission path reduces the contact impedance between each component, to improve the electro-chemical activity and flexibility of electrode.Han Jiantao
Deng in 207381477 U of CN by the way that multi-layered electrode material layer and upper clad, lower clad are successively superimposed, formed similar
The electrode slice of hamburger structure, to realize the cladding of large scale, simplification of flowsheet improves the chemical property parameter of battery.
But for these methods since active material and binder, conductive agent, collector etc. belong in conjunction with physical force, intensity is low,
It is not able to satisfy bending stability, active material still can fall off in charge and discharge process, cause chemical property to decline, Bu Nengman
The flexible battery for needing to bend for a long time in sufficient use process.
Summary of the invention
In order to solve the deficiency of prior art, the present invention provides a kind of preparation method of lithium ion battery flexible electrode,
Since active material, binder, conductive agent, elastomer, collector pass through chemical bonds in the prepared flexible electrical pole piece obtained
It being integrated, intermolecular force becomes strong, so that pole piece material living in bending or charge and discharge process is not easily to fall off, Er Qietong
Vacuum filtration is crossed, so that each section is in close contact, plays synergistic effect.Flexible electrode obtained by the present invention has good
Flexibility and chemical property are still keeping good high rate performance and cycle performance after crooked experiment.
The technical scheme of the invention to solve the technical problem is:
A kind of preparation method of flexible lithium ion battery negative electrode material is specific to make using the graphene oxide of reduction as active material
Make binder, conductive agent, elastomer and collector to be added, and react by multistep polymerization, then benefit using graphene oxide as raw material
With hydroiodic acid through reduction reaction, it is allowed to be integrated with chemical bonded refractory；The collector is conducting polymer；The binder,
Elastomer and conductive agent are with the functional group that can be reacted with graphene oxide active site.
As a preferred embodiment of the above technical solution, using graphene oxide as active material, it is firstly added conducting polymer monomer
The collector substance of form, it is aggregated to obtain graphene oxide/conducting polymer composite material；It then sequentially adds with can be with
Elastomer, conductive agent and the binder that active site is bonded on graphene oxide recycle hydroiodic acid to be gone back through reduction reaction
Former graphene oxide/conducting polymer/conductive agent/integrated composite material of binder/elastomer；Finally taken out by vacuum
Filter, dry, roll pressing obtains integrated flexible electrical pole piece.
As a preferred embodiment of the above technical solution, the functional group that can be reacted with graphene oxide active site is selected from carboxylic
One of base, hydroxyl, sulfydryl, amino, carbonyl, acyl group, ketone group, ether, thioether group, methoxyl group, sulfonic group, isocyanate group
Or it is a variety of.
As a preferred embodiment of the above technical solution, the conducting polymer be selected from polyaniline, polyacetylene, polythiophene, polypyrrole,
One of polyparaphenylene, poly-phenylene vinylene (ppv) are a variety of.
As a preferred embodiment of the above technical solution, the conducting polymer be selected from polyaniline, polyacetylene, polythiophene, polypyrrole,
One of polyparaphenylene, poly-phenylene vinylene (ppv) are a variety of.
As a preferred embodiment of the above technical solution, the binder is selected from polyvinyl alcohol, polyacrylic acid, improved polyalkene, changes
Property one of polyurethane or a variety of, the improved polyalkene is carboxylated or hydroxylated polyolefin, the modified polyurethane
For the polyurethane with carboxyl, hydroxyl, amino or isocyanate group.
As a preferred embodiment of the above technical solution, the conductive agent is by carboxylated, hydroxylating or amidized carbon nanometer
One or more of pipe, carbon fiber, superconduction carbon.
As a preferred embodiment of the above technical solution, the elastomer be with carboxyl, hydroxyl, amino, isocyanate group it is poly-
Urethane fiber-like or polyetheramides class, the racemosus crystal class fiber by carboxylated, hydroxylated nanofiber or submicron order
As a preferred embodiment of the above technical solution, specific step is as follows for the method for the present invention:
A, by graphene oxide and solvent 1:(1 ~ 20 in mass ratio) it mixes, it is uniformly dispersed, conducting polymer monomer, polymerization is added
Graphene oxide/conducting polymer composite material is generated, A is denoted as；
B, by A centrifugation, dry, the elastomer of 0.5 ~ 2.5wt% of addition, suitable solvent and catalyst, heating are allowed to react, raw
At graphene oxide/conducting polymer/elastic composite, it is denoted as B；
C, 1% ~ 10wt% scattered conductive agent is added into B, heating reaction is allowed to generate graphene oxide/conducting polymer
Object/elastomer/conductive agent composite material, is denoted as C；
D, it is added binder into C, heating reaction is allowed to generate graphene oxide/conducting polymer/elastomer/conductive agent/viscous
Agent composite material is tied, D is denoted as；
E, D is filtered by vacuum, it is 5 ~ 24 hours dry in 30 ~ 80 DEG C of baking oven；
F, the sample after drying containing D is put into hydroiodic acid from taking off on filter membrane, shading is taken out after restoring 6 ~ 18 hours, is spent
Ion water washing, drying, roll pressing obtain redox graphene/conducting polymer/conductive agent/binder/elastomer integration
Flexible electrical pole piece, be denoted as E.
As a preferred embodiment of the above technical solution, the solvent that graphene oxide is dispersed in step b is water, acetone, isopropanol, second
Alcohol, N-Methyl pyrrolidone, neopelex, Qula logical one or more of -100；Dispersed electro-conductive agent in step d
Solvent be water, ethyl alcohol, N-Methyl pyrrolidone, neopelex, Qula logical one or more of -100.
As a preferred embodiment of the above technical solution, step b, in c, d, reaction temperature is 45 ~ 120 DEG C；Reaction time be 2 ~
20h。
As a preferred embodiment of the above technical solution, be filtered by vacuum in step e miillpore filter used be selected from Kynoar filter membrane,
One of cellulose acetate sheets, composite fibre ester miillpore filter, polyamide filter membrane；The aperture of the miillpore filter be 0.1 ~
1 micron.
As a preferred embodiment of the above technical solution, the graphene oxide is made by improved Hummers method, described
The oxidant that Hummers method uses is one or more of potassium permanganate, sodium nitrate, the concentrated sulfuric acid or phosphoric acid.
Compared to the prior art, the present invention has the following advantages:
1, the prepared flexible electrical pole piece obtained is since by chemical bonding, intermolecular force becomes strong, so that pole piece is being bent
Or material living is not easily to fall off in charge and discharge process, and by vacuum filtration and roll-in, so that each section is in close contact, rises
Synergistic effect has been arrived, has enhanced the adhesion strength between electrode slice each section jointly, has improved the cycle life and safety of battery
Property；It is provided simultaneously with stronger bending stability, is still keeping good high rate performance and cycle performance after crooked experiment,
It can satisfy the needs for needing to be bent, fold for a long time in flexible battery use process.
2, conducting polymer does collector and with active material, conductive agent by chemical bonds, may be implemented close
And effective conductive contact, the electric conductivity enhancing between making, interface resistance reduce, to reduce the internal resistance of battery.
3, prepared flexible electrode tablet quality, thickness are controllable, can according to need the mass-energy for changing electrode plates
Density and volume energy density.
4, the flexible electrode prepared by the present invention passes through conducting polymer, graphene oxide, elastomer, binder, conduction
The chemical bonding of agent forms the tridimensional network to cross one another, achievees the effect that self-supporting, is not necessarily to metal afflux
Body supports, and greatly simplified the manufacture craft of battery.
5, graphene thermal diffusivity is good, and effectively heat can be discharged, and improves the safety in battery charge and discharge process；It leads
Electric polymer can also effective inhibitory activity substance expansion drop in charge and discharge process, improve cycle performance of battery and safety
Property.
Detailed description of the invention
Fig. 1 is that the integrated composite material of graphene oxide/Polymerization of Polyaniline/carbon Nanotube before film is taken out in the embodiment of the present invention 1
SEM figure.
Fig. 2 is the infrared comparison diagram of flexible electrode bonding front and back in the embodiment of the present invention 1.
Fig. 3 is redox graphene/Polymerization of Polyaniline/carbon Nanotube/polyvinyl alcohol of different multiplying in the embodiment of the present invention 1
Integrated flexible electrical pole piece SEM figure.
Fig. 4 is the film pictorial diagram after restoring and bend in example 2 of the present invention.
Specific embodiment
Invention is further explained with reference to the accompanying drawing.
Present embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Any change for being made after having read specification of the invention of member, as long as within the scope of the claims, it all will be by
The protection of Patent Law.
Embodiment 1
A kind of preparation method of lithium ion battery flexibility negative electrode material, comprising the following steps:
(1), 0.5g crystalline flake graphite is added in the 50mL concentrated sulfuric acid, 1h is stirred under the conditions of ice-water bath, 5g permanganic acid is then added
1h is stirred in potassium, continuation under the conditions of ice-water bath, then successively stirs 1.5h respectively at 40 DEG C and 90 DEG C of high temperature of medium temperature；At 90 DEG C
1000mL deionized water is added several times, 10mL hydrogen peroxide is added after complete reaction, obtains clear glassy yellow graphite oxide
Alkene dispersion liquid；After graphene oxide dispersion pickling wash clean, it is freeze-dried and powder is made；
(2), the graphene oxide after synthesizing in 0.3 gram of step (1) and is dried is taken, the hydrochloric acid of 60ml 1mol/L is dissolved in
In aqueous solution, 0.1 gram of aniline monomer is added in ultrasonic disperse 2h, and it is anti-at 0 DEG C that 0.24 gram of ammonium persulfate is added after magnetic agitation 1h
In a vacuum drying oven by product centrifugation postposition, it should be arranged 50 DEG C for 24 hours, be dried in vacuo 30 hours, it is spare；
(3), 0.3 gram of spare product of step (2) is taken, ultrasonic disperse 40 minutes in 60ml water is placed in, takes 40 milligrams of hydroxylated carbon
Nanotube is dispersed in 50ml 0.015g/ml Qula and leads in -100 aqueous solutions ultrasonic disperse 2 hours, continues to surpass after the two is mixed
Sound disperses 1 hour, and the 2ml concentrated sulfuric acid, 110 DEG C of heating water baths is added, and magnetic agitation is reacted 12 hours；
(4), it is added 8ml scattered 0.1g/ml polyvinyl alcohol into step (3) reaction system, 110 DEG C of heating water baths,
Magnetic agitation is reacted 12 hours；
(5), take solution in step (4), the gross mass of every film of control is 40mg, pours into solvent filter and filters, spend from
Sub- water washs filter cake to neutrality repeatedly, is placed in vacuum oven, 50 DEG C drying 12 hours；
(6), the sample after drying is restored from taking off to be put into hydroiodic acid on filter membrane, shading is taken out after restoring 12 hours, is spent
Ion water washing, drying, roll pressing obtain redox graphene/integrated flexible electrical of Polymerization of Polyaniline/carbon Nanotube/polyvinyl alcohol
Pole piece；
(7), finally by step (6) product directly as the negative electrode active material of test battery, lithium piece uses commercialization as anode
Electrolyte and diaphragm；Then it is assembled into 2025 button cells in argon atmosphere glove box, stands overnight, electrochemistry is carried out to it
Performance test.
Fig. 1 is the integrated composite material SEM figure of graphene oxide/Polymerization of Polyaniline/carbon Nanotube before taking out film, as seen from the figure oxygen
Graphite alkene and carbon nanotube are uniformly dispersed in the three-dimensional net structure of polyaniline, run through be staggered to form more sky mutually
Gap, structural form is more loose, is conducive to the abjection and insertion of lithium ion.
Fig. 2 is the infrared comparison diagram in flexible electrode bonding front and back, and graphene oxide is in 1720cm as seen from the figure-1On position is
C=O stretching absorbance peak on carboxyl, with the addition of hydroxyl carbon nano tube and polyvinyl alcohol, the absorption peak of hydroxyl is instead gradually
It reduces, illustrates to be reacted, due to the addition of reactant, carbon-based proportion is reduced, so back infrared intensity can be reduced.
3300cm-1On position is that polyaniline obtains secondary amine absorption peak.Both esterification has occurred in explanation, and introduces preferably
Be dispersed on polyaniline, synthesized graphene oxide/integrated composite material of Polymerization of Polyaniline/carbon Nanotube/polyvinyl alcohol.
Fig. 3 is the integrated flexible electrical pole piece SEM figure of redox graphene/Polymerization of Polyaniline/carbon Nanotube/polyvinyl alcohol,
The laminated structure of graphene and the dendritic morphology of polyaniline can be clearly seen from Fig. 3, and buckling phenomena occurs.It can be abundant
Using the high surface area of two-dimensional nano piece, while the gap that is staggered to form of nanometer sheet also can preferably alleviate lithium ion abjection and embedding
Enter bring deformation, so meet the requirement as lithium ion battery negative material, known to comparison diagram 1 by vacuum filtration so that
Each section is in close contact, so that pole piece material living in bending or charge and discharge process is not easily to fall off, and can be seen that poly-
The addition of vinyl alcohol is so that material surface smoother, shows preferable film forming.
Embodiment 2
A kind of preparation method of flexible lithium ion battery negative electrode material, comprising the following steps:
(1), 0.5g crystalline flake graphite is added in the 50mL concentrated sulfuric acid, 1h is stirred under the conditions of ice-water bath, 5g permanganic acid is then added
1h is stirred in potassium, continuation under the conditions of ice-water bath, then successively stirs 1.5h respectively at 40 DEG C and 90 DEG C of high temperature of medium temperature；At 90 DEG C
1000mL deionized water is added several times, 10mL hydrogen peroxide is added after complete reaction, obtains clear glassy yellow graphite oxide
Alkene dispersion liquid；After graphene oxide dispersion pickling wash clean, it is freeze-dried and powder is made；
(2), the graphene oxide after synthesizing in 0.3 gram of step (1) and is dried is taken, 60mlN- methyl pyrrolidone is dissolved in
In, ultrasonic disperse 2h is added 0.1 gram of aniline monomer, 0.24 gram of ammonium persulfate is added after magnetic agitation 1h and reacts at 0 DEG C for 24 hours,
In a vacuum drying oven by product centrifugation postposition, it is arranged 50 DEG C, is dried in vacuo 30 hours, it is spare；
(3), 0.3 gram of spare product of step (2) is taken, middle ultrasonic disperse 1 hour in 60mlN- methyl pyrrolidone is placed in, is added
115 milligrams of 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochlorides and 35 milligrams of n-hydroxysuccinimides continue to surpass
Sound disperses 20 minutes, and centrifugation after 7.5 milligrams of polyetherimide react at room temperature 48 hours, drying is added；
(4) 0.3 gram of product of step (3) are taken, ultrasonic disperse 1 hour in 60mlN- methyl pyrrolidone is placed in, take 40 milligrams of hydroxyls
The carbon nanotube of change is dispersed in ultrasonic disperse 2 hours in 60mlN- methyl pyrrolidone, continues ultrasonic disperse 1 after the two is mixed
Hour, the 2ml concentrated sulfuric acid, 110 DEG C of heating water baths is added, magnetic agitation is reacted 12 hours；
(5), it is added 8ml scattered 0.05g/ml polyacrylic acid into step (4) reaction system, 110 DEG C of heating water baths,
Magnetic agitation is reacted 12 hours；
(6), take solution in step (5), the gross mass of every film of control is 40mg, pours into solvent filter and filters, spend from
Sub- water washs filter cake to neutrality repeatedly, is placed in vacuum oven, 50 DEG C drying 12 hours；
(7), the sample after drying is restored from taking off to be put into hydroiodic acid on filter membrane, shading is taken out after restoring 12 hours, is spent
Ion water washing, drying, roll pressing obtain redox graphene/polyaniline/polyetherimide/carbon nanotube/polypropylene acid one
The flexible electrical pole piece of body.Fig. 4 is the film pictorial diagram after reduction and bending.
Embodiment 3
A kind of preparation method of flexible lithium ion battery negative electrode material, comprising the following steps:
(1), 0.5g crystalline flake graphite is added in the 50mL concentrated sulfuric acid, 1h is stirred under the conditions of ice-water bath, 5g permanganic acid is then added
1h is stirred in potassium, continuation under the conditions of ice-water bath, then successively stirs 1.5h respectively at 40 DEG C and 90 DEG C of high temperature of medium temperature；At 90 DEG C
1000mL deionized water is added several times, 10mL hydrogen peroxide is added after complete reaction, obtains clear glassy yellow graphite oxide
Alkene dispersion liquid；After graphene oxide dispersion pickling wash clean, it is freeze-dried and powder is made；
(2), the graphene oxide after synthesizing in 0.3 gram of step (1) and is dried is taken, is dissolved in 60ml deionized water, is surpassed
Sound disperses 2h, under stiring, puts into monomer benzene, catalyst AlCl by a certain percentage3With oxidant CuCl, it is slowly warming up to 30
DEG C, constant temperature is then kept, after the induction period of certain time, reaction is with the progress of faster speed, and color is by colorless and transparent change
Become coffee-like again for light brown, after reaction 2 hours, by reaction product cooling, is filtered, washed, drying for standby；
(3), 0.3 gram of spare product of step (2) is taken, ultrasonic disperse 1 hour in 60ml deionized water is placed in, takes 40 milligrams of hydroxyls
The carbon nanotube of change is dispersed in ultrasonic disperse 2 hours in 60ml water, continues ultrasonic disperse 1 hour after the two is mixed, and 2ml is added
The concentrated sulfuric acid, 110 DEG C of heating water baths, magnetic agitation are reacted 12 hours；
(4), it is added 8ml scattered 0.1g/ml polyvinyl alcohol into step (3) reaction system, 110 DEG C of heating water baths,
Magnetic agitation is reacted 12 hours；
(5), solution in step (4) is taken, the gross mass of every film of control is 40mg, pours into solvent filter and filters in batches, is used
Deionized water washs filter cake to neutrality repeatedly, is placed in vacuum oven, 50 DEG C drying 12 hours；
(6), the sample after drying is restored from taking off to be put into hydroiodic acid on filter membrane, shading is taken out after restoring 12 hours, is spent
Ion water washing, drying, roll pressing obtain redox graphene/integrated flexibility of polyparaphenylene/carbon nanotube/polyvinyl alcohol
Electrode slice.
Claims (10)
1. a kind of preparation method of flexible lithium ion battery negative electrode material, special using the graphene oxide of reduction as active material
Sign is: binder, conductive agent, elastomer and collector being added in graphene oxide, and is reacted by multistep polymerization, then benefit
With hydroiodic acid through reduction reaction, it is allowed to be integrated with chemical bonded refractory；The collector is conducting polymer；The binder,
Elastomer and conductive agent are with the functional group that can be reacted with graphene oxide active site.
2. a kind of preparation method of flexible lithium ion battery negative electrode material according to claim 1, it is characterised in that: described
The functional group that can be reacted with graphene oxide active site is selected from carboxyl, hydroxyl, sulfydryl, amino, carbonyl, acyl group, ketone group, ether
One of base, thioether group, methoxyl group, sulfonic group, isocyanate group are a variety of.
3. a kind of preparation method of flexible lithium ion battery negative electrode material according to claim 1, it is characterised in that: described
Conducting polymer is selected from one of polyaniline, polyacetylene, polythiophene, polypyrrole, polyparaphenylene, poly-phenylene vinylene (ppv) or more
Kind.
4. a kind of preparation method of flexible lithium ion battery negative electrode material according to claim 1, it is characterised in that: described
Binder is selected from one of polyvinyl alcohol, polyacrylic acid, improved polyalkene, modified polyurethane or a variety of, the modified polyolefin
Hydrocarbon is carboxylated or hydroxylated polyolefin, and the modified polyurethane is poly- with carboxyl, hydroxyl, amino or isocyanate group
Urethane.
5. a kind of preparation method of flexible lithium ion battery negative electrode material according to claim 1, it is characterised in that: described
Conductive agent is by one or more of carboxylated, hydroxylating or amidized carbon nanotube, carbon fiber, superconduction carbon.
6. a kind of preparation method of flexible lithium ion battery negative electrode material according to claim 1, it is characterised in that: described
Elastomer be with carboxyl, hydroxyl, amino, isocyanate group polyurethane fiber class or polyetheramides class, by carboxylated, hydroxyl
The nanofiber of base or the racemosus crystal class fiber of submicron order.
7. a kind of preparation method of flexible lithium ion battery negative electrode material according to claim 1, the following steps are included:
A, by graphene oxide and solvent 1:(1 ~ 20 in mass ratio) it mixes, it is uniformly dispersed, conducting polymer monomer, polymerization is added
Graphene oxide/conducting polymer composite material is generated, A is denoted as；
B, by A centrifugation, dry, the elastomer of 0.5 ~ 2.5wt% of addition, suitable solvent and catalyst, heating are allowed to react, raw
At graphene oxide/conducting polymer/elastic composite, it is denoted as B；
C, 1% ~ 10wt% scattered conductive agent is added into B, heating reaction is allowed to generate graphene oxide/conducting polymer
Object/elastomer/conductive agent composite material, is denoted as C；
D, it is added binder into C, heating reaction is allowed to generate graphene oxide/conducting polymer/elastomer/conductive agent/viscous
Agent composite material is tied, D is denoted as；
E, D is filtered by vacuum, it is 5 ~ 24 hours dry in 30 ~ 80 DEG C of baking oven；
F, the sample after drying containing D is put into hydroiodic acid from taking off on filter membrane, shading is taken out after restoring 6 ~ 18 hours, is spent
Ion water washing, drying, roll pressing obtain redox graphene/conducting polymer/conductive agent/binder/elastomer integration
Flexible electrical pole piece, be denoted as E.
8. a kind of preparation method of flexible lithium ion battery negative electrode material according to claim 7, it is characterised in that: step
The solvent for dispersing graphene oxide in rapid b is water, acetone, isopropanol, ethyl alcohol, N-Methyl pyrrolidone, dodecyl benzene sulfonic acid
Sodium, Qula logical one or more of -100；In step d the solvent of dispersed electro-conductive agent be water, ethyl alcohol, N-Methyl pyrrolidone,
Neopelex, Qula logical one or more of -100.
9. a kind of preparation method of flexible lithium ion battery negative electrode material according to claim 7, it is characterised in that: step
In rapid b, c, d, reaction temperature is 45 ~ 120 DEG C；Reaction time is 2 ~ 20h.
10. a kind of preparation method of flexible lithium ion battery negative electrode material according to claim 7, it is characterised in that: step
Miillpore filter used is filtered by vacuum in rapid e and is selected from Kynoar filter membrane, cellulose acetate sheets, the filter of composite fibre ester micropore
One of film, polyamide filter membrane；The aperture of the miillpore filter is 0.1 ~ 1 micron.
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